WO2018230233A1 - マスクブランク、位相シフトマスク及び半導体デバイスの製造方法 - Google Patents

マスクブランク、位相シフトマスク及び半導体デバイスの製造方法 Download PDF

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Publication number
WO2018230233A1
WO2018230233A1 PCT/JP2018/018872 JP2018018872W WO2018230233A1 WO 2018230233 A1 WO2018230233 A1 WO 2018230233A1 JP 2018018872 W JP2018018872 W JP 2018018872W WO 2018230233 A1 WO2018230233 A1 WO 2018230233A1
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WIPO (PCT)
Prior art keywords
phase shift
film
light
lower layer
upper layer
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PCT/JP2018/018872
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English (en)
French (fr)
Japanese (ja)
Inventor
雅広 橋本
博明 宍戸
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Hoya株式会社
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Application filed by Hoya株式会社 filed Critical Hoya株式会社
Priority to US16/622,802 priority Critical patent/US11048160B2/en
Priority to KR1020197035396A priority patent/KR102592274B1/ko
Priority to SG11201912030PA priority patent/SG11201912030PA/en
Priority to CN201880039083.1A priority patent/CN110770652B/zh
Publication of WO2018230233A1 publication Critical patent/WO2018230233A1/ja
Priority to US17/331,955 priority patent/US20210286254A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/32—Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
    • G03F1/84—Inspecting
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment

Definitions

  • the present invention relates to a mask blank for a phase shift mask, a phase shift mask, and a method for manufacturing a semiconductor device using the phase shift mask.
  • a fine pattern is formed using a photolithography method.
  • a number of substrates called transfer masks are used.
  • This transfer mask is generally a transparent glass substrate provided with a fine pattern made of a metal thin film or the like.
  • a photolithography method is also used in the production of the transfer mask.
  • a halftone phase shift mask is known in addition to a binary mask having a light-shielding film pattern made of a chromium-based material on a conventional translucent substrate.
  • This halftone type phase shift mask is provided with a phase shift film pattern on a translucent substrate.
  • This phase shift film transmits light at an intensity that does not substantially contribute to exposure, and causes the light transmitted through the phase shift film to have a predetermined phase difference with respect to light that has passed through the air by the same distance. It has a function, and this causes a so-called phase shift effect.
  • Patent Document 1 when an exposure apparatus is used to perform exposure transfer of a transfer mask pattern onto a resist film on a single semiconductor wafer, the transfer mask pattern is different from that of the resist film.
  • exposure transfer is repeatedly performed at a position.
  • the repeated exposure transfer to the resist film is performed without any interval.
  • the exposure apparatus is provided with an aperture so that exposure light is irradiated only to a region (transfer region) where a transfer pattern of the transfer mask is formed.
  • there is a limit to the accuracy with which the exposure light is covered (shielded) by the aperture and it is difficult to avoid that the exposure light leaks outside the transfer region of the transfer mask.
  • the outer peripheral area of the area where the transfer pattern is formed in the transfer mask is affected by the exposure light transmitted through the outer peripheral area when the exposure film is exposed and transferred to the resist film on the semiconductor wafer. Therefore, it is required to ensure an optical density (OD: Optical Dimension) that is equal to or higher than a predetermined value.
  • OD Optical Dimension
  • the OD is 3 or more (transmittance of about 0.1% or less), and at least about 2.8 (transmittance of about 0.16%) is required. Has been.
  • the phase shift film of the halftone phase shift mask has a function of transmitting the exposure light with a predetermined transmittance, and this phase shift film alone is an optical element required for the outer peripheral region of the transfer mask. It is difficult to ensure the concentration.
  • a light semi-transmissive layer is formed by laminating a light shielding layer (light shielding band) on the light semi-transmissive layer in the outer peripheral region. An optical density equal to or higher than the above predetermined value is ensured by a laminated structure of a layer and a light shielding layer.
  • Patent Document 2 as a mask blank of a halftone phase shift mask, a halftone phase shift film made of a metal silicide-based material on a translucent substrate, a light-shielding film made of a chromium-based material, A mask blank having a structure in which an etching mask film made of an inorganic material is laminated has been known.
  • an etching mask film is patterned by dry etching with a fluorine-based gas using a resist pattern formed on the surface of the mask blank as a mask.
  • the light shielding film is patterned by dry etching with a mixed gas of chlorine and oxygen using the etching mask film pattern as a mask, and the phase shift film is patterned by dry etching with a fluorine-based gas using the light shielding film pattern as a mask.
  • the conventional light-shielding film is based on the assumption that exposure light that has passed through the phase-shift film at a predetermined transmittance enters from the surface of the light-shielding film on the phase-shift film side and exits from the surface opposite to the phase-shift film.
  • the light shielding performance (optical density) is determined as follows. However, when the exposure light of the above complicated illumination system is irradiated to the phase shift mask, the exposure light that has passed through the phase shift film and has entered from the surface of the light shielding film on the phase shift film side has a light shielding band. It has been found that the emission from the pattern side wall is more likely to occur than in the past.
  • the amount of exposure light (leakage light) emitted from the pattern side wall is not sufficiently attenuated, so that the resist film provided on the semiconductor wafer or the like is slightly exposed. If the region where the transfer pattern of the resist film is arranged is exposed to light even slightly, the CD (Critical Dimension) of the resist pattern formed by developing the transfer pattern exposed in the region is greatly reduced.
  • FIG. 3 is an explanatory diagram when the transfer pattern of the phase shift mask is transferred four times to the resist film on the semiconductor wafer.
  • the image I 1 is an image transferred when the transfer pattern of the phase shift mask is transferred once by exposure. The same applies to the images I 2 , I 3 , and I 4 .
  • Image p 1a ⁇ p 1e is a pattern transferred on the same exposure and transfer the same image p 2a ⁇ p 2e, the image p 3a ⁇ p 3e, even image p 4a ⁇ p 4e.
  • Images S 1 , S 2 , S 3 , and S 4 are images to which the light shielding band pattern of the phase shift mask is transferred. As shown in FIG.
  • S 12 , S 13 , S 24 , and S 34 are areas where the transfer images of the two light-shielding bands are superimposed and transferred, and S 1234 is the image where the transfer images of the four light-shielding bands are superimposed and transferred. Area.
  • the transfer pattern of the phase shift film can be arranged up to the vicinity of the light-shielding band (image S 1 ). It is increasing.
  • the arrangement of the plurality of transfer patterns that are repeatedly transferred to the resist film on the semiconductor wafer has a positional relationship in which adjacent light-shielding band patterns overlap.
  • the region where the light-shielding band pattern is overlapped and exposed and transferred is used as a cutting allowance when the chip is formed after each chip is formed on the semiconductor wafer.
  • the phase shift film is often formed of a material containing silicon, and the light shielding film is formed of a material containing chromium (chromium-based material) having high etching selectivity with the phase shift film.
  • the light shielding film made of a chromium-based material is patterned by dry etching using a mixed gas of chlorine-based gas and oxygen gas, but the resist film has low resistance to dry etching using a mixed gas of chlorine-based gas and oxygen gas. For this reason, when the thickness of the light shielding film is increased, the thickness of the resist film needs to be significantly increased. However, when a fine pattern is formed on such a resist film, problems such as collapse or missing of the resist pattern are likely to occur.
  • Patent Document 2 it is possible to reduce the thickness of the resist film by providing a hard mask film made of a material containing silicon on a light shielding film made of a chromium-based material. .
  • a light shielding film made of a chromium-based material is patterned by dry etching using a mixed gas of chlorine-based gas and oxygen gas, the etching tends to proceed toward the pattern side wall.
  • dry etching using a hard mask film having a fine pattern as a mask is performed on the light shielding film, if the thickness of the light shielding film is large, the amount of side etching tends to increase, and the fineness formed on the light shielding film.
  • the CD accuracy of the pattern tends to decrease.
  • a decrease in CD accuracy of the fine pattern of the light shielding film leads to a decrease in CD accuracy of the fine pattern formed on the phase shift film by dry etching using the fine pattern of the light shielding film as a mask.
  • a cleaning process is performed on the light-shielding film after patterning.
  • the film thickness of the light-shielding film is large, there is a problem that the pattern of the light-shielding film tends to fall during the cleaning.
  • the present invention is such that a phase shift film formed of a material containing silicon and a light shielding film including a layer formed of a material containing chromium are stacked in this order on a light-transmitting substrate.
  • a mask blank having a structure a phase shift mask manufactured from the mask blank is set in an exposure apparatus of a complicated illumination system to which SMO is applied and provided on a semiconductor wafer or the like to be transferred. Even when the transferred resist film is exposed and transferred, the optical density higher than the conventional one is shielded from the phase shift film so that the fine pattern formed on the resist film after the development processing has high CD accuracy.
  • a first object is to provide a mask blank having a laminated structure of films.
  • the second object of the present invention is to provide a mask blank in which the CD accuracy of the fine pattern formed on the light shielding film by dry etching is high and the occurrence of the tilting of the light shielding film pattern is suppressed.
  • the present invention also relates to a phase shift mask manufactured using this mask blank. Even when the phase shift mask is set in an exposure apparatus of a complicated illumination system and exposure transfer is performed on a resist film, the development is performed. It is possible to form a light-shielding band with a higher optical density than before so that the fine pattern formed on the resist film after processing has high CD accuracy, and it is possible to form a fine pattern with high precision on the phase shift film.
  • An object of the present invention is to provide a simple phase shift mask.
  • Another object of the present invention is to provide a semiconductor device manufacturing method using the phase shift mask.
  • the present invention has the following configuration as means for solving the above problems.
  • the optical density with respect to the exposure light of the ArF excimer laser in the laminated structure of the phase shift film and the light shielding film is 3.5 or more
  • the light-shielding film has a structure in which a lower layer and an upper layer are laminated from the translucent substrate side,
  • the lower layer is made of a material containing chromium and having a total content of chromium, oxygen, nitrogen and carbon of 90 atomic% or more
  • the upper layer is made of a material containing metal and silicon, and the total content of metal and silicon is 80 atomic% or more,
  • the upper layer the extinction coefficient k U with respect to the exposure light, the mask blank and greater than the extinction coefficient k L with respect to the lower layer of the exposure light.
  • the optical density with respect to the exposure light of the ArF excimer laser in the laminated structure of the phase shift film and the light shielding film is 3.5 or more
  • the light-shielding film has a structure in which a lower layer and an upper layer are laminated from the translucent substrate side,
  • the lower layer is made of a material containing chromium and having a total content of chromium, oxygen, nitrogen and carbon of 90 atomic% or more
  • the upper layer is made of a material containing metal and silicon, and the total content of metal and silicon is 80 atomic% or more,
  • the upper layer the extinction coefficient k U with respect to the exposure light in a phase shift mask being larger than the extinction coefficient k L with respect to the lower layer of the exposure light.
  • (Configuration 12) Refractive index n U with respect to the exposure light of the upper layer, the lower layer of the smaller than the refractive index n L with respect to the exposure light, the refractive index n of the refractive index n U with respect to the exposure light of the upper layer with respect to the exposure light of the lower layer phase shift mask according to any one of configurations 9, wherein 11 of the ratio n U / n L divided by L is 0.8 or more.
  • the refractive index n L of the lower layer is 2.0 or less
  • a phase shift mask according to the structure 12 refractive index n U of the upper layer is characterized in that less than 2.0.
  • (Configuration 14) 14 14.
  • the mask blank of the present invention Since the mask blank of the present invention has a high optical density suitable for SMO with an optical density of 3.5 or more with respect to the exposure light of the ArF excimer laser in the laminated structure of the phase shift film and the light shielding film, this mask blank is used. Even when the manufactured phase shift mask is set in an exposure apparatus of a complicated illumination system to which SMO is applied and exposure transfer is performed on a resist film to be transferred, the resist after development processing The CD accuracy of a fine pattern formed on the film can be increased.
  • the mask blank of the present invention has a high CD accuracy of the formed fine pattern when the fine pattern is formed on the light shielding film by dry etching, and the fine pattern of the formed light shielding film falls down by washing or the like. Can be sufficiently suppressed.
  • the phase shift mask of the present invention is manufactured using the mask blank of the present invention. Therefore, even when the phase shift mask is set in an exposure apparatus of a complicated illumination system to which SMO is applied and the exposure transfer is performed on the resist film of the transfer target, The CD accuracy of the fine pattern formed on the resist film can be increased. Moreover, since the phase shift mask of this invention manufactures a phase shift mask using the mask blank of this invention, a fine pattern can be accurately formed in a phase shift film. Furthermore, the semiconductor device manufacturing method using the phase shift mask of the present invention makes it possible to transfer a fine pattern to a resist film on a semiconductor wafer with good CD accuracy.
  • the inventor sets a phase shift mask in an exposure apparatus of a complicated illumination system to which SMO is applied, and performs exposure transfer on a resist film provided on a semiconductor wafer or the like to be transferred.
  • the optical density in the laminated structure of the phase shift film and the light-shielding film necessary for the fine pattern formed on the resist film after the development processing to have high CD accuracy was studied.
  • an optical density (hereinafter simply referred to as optical density) with respect to ArF excimer laser exposure light (hereinafter referred to as ArF exposure light) in the laminated structure of the phase shift film and the light shielding film is required to be 3.5 or more. I found out.
  • the transmittance of the phase shift film with respect to ArF exposure light is 6% (optical density is about 1.2), which is a widely used transmittance.
  • the optical density of the light shielding film with respect to ArF exposure light needs to be 2.3 or more.
  • the optical density was increased to 2.3 or more by increasing the thickness of the light-shielding film, it was necessary to significantly increase the thickness of the resist pattern, so that a fine pattern was formed on the light-shielding film by dry etching. It was difficult.
  • a hard mask film made of a silicon-based material was provided on the light shielding film, and an attempt was made to form a fine pattern on the light shielding film by dry etching using the hard mask film on which the fine pattern was formed as a mask.
  • the amount of side etching generated when a fine pattern is formed on the light shielding film is large, and the CD accuracy of the fine pattern formed on the light shielding film is lowered.
  • the fine pattern is formed on the light shielding film and then washed, a phenomenon that the light shielding film pattern is detached occurs, and it is difficult to form the fine pattern on the light shielding film with this method. It was.
  • a light-shielding film is formed with a material having an extremely high chromium content such that the optical density is 2.3 or more, a hard mask film of a silicon-based material is laminated on the light-shielding film, and a fine pattern is formed on the light-shielding film.
  • this light-shielding film has a very slow etching rate for dry etching with a mixed gas of chlorine-based gas and oxygen gas, resulting in low CD uniformity in the plane of the pattern formed on the light-shielding film.
  • the light shielding film a laminated structure of a lower layer of a chromium-based material and an upper layer of a metal silicide-based material.
  • the lower layer of the light-shielding film By forming the lower layer of the light-shielding film on the phase shift film side with a chromium-based material, it has high etching resistance against dry etching with a fluorine-based gas performed when forming a fine pattern on the phase shift film. It can have a function as a hard mask.
  • the phase shift film has high etching resistance against dry etching with a mixed gas of chlorine-based gas and oxygen gas, which is performed when removing the light shielding film, and therefore the influence on the phase shift film when removing the light shielding film.
  • the upper layer of the light shielding film by forming the upper layer of the light shielding film with a metal silicide material, it has high etching resistance against dry etching with a mixed gas of chlorine gas and oxygen gas, which is performed when forming a fine pattern below the light shielding film. It can have a function as a hard mask.
  • the upper layer of the light shielding film can be removed at the same time during dry etching with a fluorine-based gas performed when forming a fine pattern on the phase shift film.
  • the lower layer of the light shielding film contains an element (such as silicon) that greatly reduces the etching rate with respect to dry etching with a mixed gas of chlorine-based gas and oxygen gas.
  • the lower layer of the light-shielding film is made of a material containing chromium and having a total content of chromium, oxygen, nitrogen and carbon of 90 atomic% or more. From the above situation, it is difficult to increase the chromium content in the chromium-based material forming the lower layer of the light-shielding film, and the extinction coefficient k L for the lower ArF exposure light (hereinafter simply referred to as the extinction coefficient k L ).
  • the upper layer of the light shielding film is often made of a material having a smaller extinction coefficient k than the lower layer in consideration of providing an antireflection function.
  • recent improvements in the performance of exposure apparatuses have eased restrictions on surface reflectance in regions outside the transfer pattern region (including regions where light-shielding bands are formed). Therefore, we decided to such larger configurations also upper layer of the extinction coefficient k U lower layer of the extinction coefficient k L of the light-shielding film.
  • the upper layer of the light shielding film is required to function as a hard mask when the lower layer of the chromium-based material is patterned by dry etching using a mixed gas of chlorine-based gas and oxygen gas.
  • a conventional hard mask film made of a silicon-based material has been emphasized to improve etching selectivity with respect to a thin film of a chromium-based material, and a silicon material containing a relatively large amount of oxygen or nitrogen is used.
  • the content of oxygen and nitrogen in the upper layer of the metal silicide material is lower than that of the conventional material, and etching for dry etching with a mixed gas of chlorine gas and oxygen gas between the lower layer of the chromium material. The selectivity was verified.
  • the upper layer of the light-shielding film is made of a material containing metal and silicon, and the total content of metal and silicon is 80 atomic%.
  • the mask blank of the present invention has been completed. Specifically, it is a mask blank having a structure in which a phase shift film and a light shielding film are laminated in this order on a translucent substrate, and the exposure light of the ArF excimer laser in the laminated structure of the phase shift film and the light shielding film.
  • the optical density is 3.5 or more
  • the light shielding film has a structure in which a lower layer and an upper layer are laminated from the translucent substrate side, the lower layer contains chromium, and the total content of chromium, oxygen, nitrogen, and carbon is
  • the upper layer contains a metal and silicon, the total content of the metal and silicon is 80 atom% or more, and the extinction coefficient k U for the exposure light of the upper layer is: It is characterized by being larger than the extinction coefficient k L for the exposure light of the lower layer.
  • FIG. 1 shows a schematic configuration of an embodiment of a mask blank.
  • a mask blank 100 shown in FIG. 1 has a configuration in which a phase shift film 2, a lower layer 31 of a light shielding film 3, and an upper layer 32 of the light shielding film 3 are laminated in this order on one main surface of the translucent substrate 1.
  • the mask blank 100 may have a configuration in which a resist film is laminated on the upper layer 32 as necessary.
  • the mask blank 100 is at least required to have a laminated structure of the phase shift film 2 and the light shielding film 3 and have an optical density of 3.5 or more with respect to ArF exposure light.
  • the mask blank 100 is a laminated structure of the phase shift film 2 and the light-shielding film 3, and the optical density with respect to ArF exposure light is more preferably 3.8 or more, and further preferably 4.0 or more.
  • the optical density with respect to ArF exposure light is more preferably 3.8 or more, and further preferably 4.0 or more.
  • the translucent substrate 1 is made of a material having good transparency to exposure light used in an exposure process in lithography.
  • synthetic quartz glass, aluminosilicate glass, soda lime glass, low thermal expansion glass (such as SiO 2 —TiO 2 glass), and other various glass substrates can be used.
  • a substrate using synthetic quartz glass has high transparency to ArF exposure light, it can be suitably used as the light-transmitting substrate 1 of the mask blank 100.
  • the exposure process in lithography mentioned here is an exposure process in lithography performed using the phase shift mask produced using this mask blank 100, and exposure light is ArF used in this exposure process below.
  • Excimer laser (wavelength: 193 nm).
  • the phase shift film 2 transmits ArF exposure light with an intensity that does not substantially contribute to exposure, and exposure light that has passed through the air at the same distance as the thickness of the phase shift film 2 with respect to the transmitted ArF exposure light. Has a function of causing a predetermined phase difference between the two. Specifically, by patterning the phase shift film 2, a portion where the phase shift film 2 remains and a portion where the phase shift film 2 does not remain are formed, and the phase shift is applied to the exposure light transmitted through the portion where the phase shift film 2 is not present. The phase of the light transmitted through the film 2 (light with an intensity that does not substantially contribute to exposure) is substantially reversed.
  • the phase shift film 2 has a transmittance with respect to ArF exposure light of preferably 1% or more, and more preferably 2% or more.
  • the phase shift film 2 preferably has a transmittance with respect to ArF exposure light of 35% or less, and more preferably 30% or less.
  • the phase shift film 2 preferably has the above phase difference of 150 degrees or more, and more preferably 160 degrees or more. Further, the phase shift film 2 preferably has a phase difference of 200 degrees or less, and more preferably 190 degrees or less.
  • the phase shift film 2 is made of a material containing silicon (Si).
  • the phase shift film 2 is preferably formed of a material containing nitrogen (N) in addition to silicon.
  • Such a phase shift film 2 can be patterned by dry etching using a fluorine-based gas, and has sufficient etching selectivity with respect to a lower layer 31 of a Cr-based material constituting a light shielding film 3 described later.
  • the phase shift film 2 is preferably formed of a material made of silicon and nitrogen, or a material containing one or more elements selected from a metalloid element and a nonmetal element in a material made of silicon and nitrogen.
  • the phase shift film 2 may contain any metalloid element in addition to silicon and nitrogen. Among these metalloid elements, inclusion of one or more elements selected from boron (B), germanium (Ge), antimony (Sb), and tellurium (Te) can increase the conductivity of silicon used as a sputtering target. It is preferable because it can be expected.
  • the phase shift film 2 may contain any nonmetallic element in addition to silicon and nitrogen.
  • the nonmetallic element in the present invention includes a nonmetallic element in a narrow sense (nitrogen (N), carbon (C), oxygen (O), phosphorus (P), sulfur (S), selenium (Se)), halogen, and The thing containing noble gas.
  • these nonmetallic elements it is preferable to include one or more elements selected from carbon, fluorine (F), and hydrogen (H).
  • the phase shift film 2 may contain a noble gas (also referred to as a rare gas; hereinafter the same in this specification).
  • the noble gas is an element that can increase the deposition rate and improve the productivity by being present in the deposition chamber when the phase shift film 2 is deposited by reactive sputtering.
  • this noble gas is turned into plasma and collides with the target, the target constituent element pops out from the target and reaches the translucent substrate 1 while adhering to the translucent substrate 1 while taking in the reactive gas.
  • a phase shift film 2 is formed on the conductive substrate 1.
  • the noble gas in the film formation chamber is slightly taken in until the target constituent element jumps out of the target and adheres to the translucent substrate 1.
  • Preferred examples of the noble gas required for this reactive sputtering include argon (Ar), krypton (Kr), and xenon (Xe).
  • Ar argon
  • Kr krypton
  • Xe xenon
  • helium (He) and neon (Ne) having a small atomic weight can be actively incorporated into the phase shift film.
  • the phase shift film 2 may further contain a metal element as long as it can be patterned by dry etching using a fluorine-based gas.
  • the metal elements to be contained are molybdenum (Mo), tungsten (W), titanium (Ti), tantalum (Ta), zirconium (Zr), hafnium (Hf), niobium (Nb), vanadium (V), cobalt (Co ), Chromium (Cr), nickel (Ni), ruthenium (Ru), tin (Sn), and aluminum (Al).
  • the thickness of the phase shift film 2 is preferably 90 nm or less. If the thickness of the phase shift film 2 is greater than 90 nm, the time required for patterning by dry etching with a fluorine-based gas becomes longer.
  • the phase shift film 2 is more preferably 80 nm or less in thickness.
  • the phase shift film 2 preferably has a thickness of 40 nm or more. If the thickness of the phase shift film 2 is less than 40 nm, the predetermined transmittance and phase difference required for the phase shift film may not be obtained.
  • the light shielding film 3 has a configuration in which a lower layer 31 and an upper layer 32 are laminated in this order from the phase shift film 2 side.
  • the lower layer 31 contains chromium and is formed of a material having a total content of chromium, oxygen, nitrogen, and carbon of 90 atomic% or more.
  • the lower layer 31 is preferably formed of a material having a total content of chromium, oxygen, nitrogen, and carbon of 95 atomic% or more, and more preferably formed of a material having 98 atomic% or more. This is because in order to increase the etching rate for dry etching using a mixed gas of chlorine-based gas and oxygen gas, it is preferable to reduce the content of elements other than the above (particularly silicon).
  • the lower layer 31 may contain a metal element, a semi-metal element, and a non-metal element other than the above constituent elements as long as it satisfies the above-mentioned total content range.
  • the metal element in this case include molybdenum, indium, and tin.
  • the metalloid element in this case include boron and germanium.
  • the nonmetallic element in this case include non-metallic elements in a narrow sense (phosphorus, sulfur, selenium), halogen (fluorine, chlorine, etc.), and noble gases (helium, neon, argon, krypton, xenon, etc.).
  • the noble gas is an element that is slightly taken into the film when the lower layer 31 is formed by a sputtering method, and is also an element that may be beneficial if it is actively contained in the layer.
  • content in the lower layer 31 is calculated
  • the lower layer 31 is preferably formed of a material containing chromium and having a total content of chromium, oxygen, and carbon of 90 atomic% or more.
  • the lower layer 31 is preferably formed of a material having a total content of chromium, oxygen and carbon of 95 atomic% or more, and more preferably formed of a material having 98 atomic% or more.
  • the nitrogen content in the lower layer 31 increases, the etching rate for dry etching using a mixed gas of chlorine-based gas and oxygen gas increases, but the side etching amount also increases.
  • the lower layer 31 preferably has a nitrogen content of less than 10 atomic%, more preferably 5 atomic% or less, and even more preferably 2 atomic% or less.
  • the lower layer 31 is substantially composed of chromium, oxygen, and carbon, and includes an embodiment that does not substantially contain nitrogen.
  • the lower layer 31 preferably has a chromium content of 50 atomic% or more.
  • a material having a high optical density is selected for the upper layer 32, but it is preferable to secure a certain level of optical density for the lower layer 31. Another reason is to suppress side etching that occurs when the lower layer 31 is patterned by dry etching.
  • the lower layer 31 preferably has a chromium content of 80 atomic% or less, and more preferably 75 atomic% or less. This is to ensure a sufficient etching rate when the light shielding film 3 is patterned by dry etching.
  • the lower layer 31 preferably has an oxygen content of 10 atomic% or more, and more preferably 15 atomic% or more. This is to ensure a sufficient etching rate when the light shielding film 3 is patterned by dry etching.
  • the lower layer 31 preferably has an oxygen content of 50 atomic% or less, more preferably 40 atomic% or less, and even more preferably 35 atomic% or less. This is because, similarly to the above, it is preferable to secure a certain optical density in the lower layer 31 as well. Another reason is to suppress side etching that occurs when the lower layer 31 is patterned by dry etching.
  • the lower layer 31 preferably has a carbon content of 10 atomic% or more. This is to suppress side etching that occurs when the lower layer 31 is patterned by dry etching.
  • the lower layer 31 preferably has a carbon content of 30 atomic% or less, more preferably 25 atomic% or less, and even more preferably 20 atomic% or less. This is to ensure a sufficient etching rate when the light shielding film 3 is patterned by dry etching.
  • the lower layer 31 preferably has a difference in content of each element constituting the lower layer 31 in the film thickness direction of less than 10%. This is to reduce variations in the etching rate in the film thickness direction when the lower layer 31 is patterned by dry etching.
  • the lower layer 31 preferably has a thickness larger than 15 nm, more preferably 18 nm or more, and further preferably 20 nm or more. On the other hand, the lower layer 31 preferably has a thickness of 60 nm or less, more preferably 50 nm or less, and further preferably 45 nm or less.
  • a material having a high optical density is selected for the upper layer 32, but there is a limit to increasing the contribution of the upper layer 32 to the optical density required for the entire light shielding film 3. For this reason, it is necessary to ensure a certain optical density even in the lower layer 31.
  • the lower layer 31 needs to increase the etching rate for dry etching using a mixed gas of chlorine-based gas and oxygen gas, there is a limit to improving the light shielding performance. Therefore, the lower layer 31 needs to have a predetermined thickness or more. On the other hand, if the lower layer 31 is too thick, it is difficult to suppress the occurrence of side etching. The range of the thickness of the lower layer 31 takes these restrictions into consideration.
  • the upper layer 32 includes a metal and silicon, and is formed of a material having a total content of metal and silicon of 80 atomic% or more.
  • the upper layer 32 is preferably formed of a material having a total content of metal and silicon of 85 atomic% or more, and more preferably formed of a material of 90 atomic% or more.
  • metal and silicon are elements that enhance the light shielding performance of the upper layer 32 against ArF exposure light.
  • high resistance to dry etching by a mixed gas of chlorine-based gas and oxygen gas which is performed when forming a fine pattern in the lower layer 31. It has been found that it can function as a hard mask.
  • the upper layer 32 opposite to the phase shift film 2 is a surface that comes into contact with the atmosphere, the surface layer including the surface is likely to be oxidized. For this reason, it is difficult to form the entire upper layer 32 with only metal and silicon.
  • the upper layer 32 has a higher light shielding performance than the lower layer 31.
  • the upper layer 32 is required to be formed of a material having a total content of metal and silicon of 80 atomic% or more in the average of the entire layer, and is preferably 85 atomic% or more, More preferably, it is 90 atomic% or more.
  • the metal elements contained in the upper layer 32 are molybdenum (Mo), tungsten (W), titanium (Ti), tantalum (Ta), zirconium (Zr), hafnium (Hf), niobium (Nb), vanadium (V), One or more metal elements from cobalt (Co), chromium (Cr), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), indium (In), tin (Sn), and aluminum (Al) Is preferably selected.
  • the metal element contained in the upper layer 32 is more preferably tantalum.
  • Tantalum has a high atomic weight and high light shielding performance, and has a high resistance to a cleaning liquid used in a cleaning process performed in the course of manufacturing a phase shift mask from a mask blank and a cleaning liquid used in cleaning performed on a phase shift mask. It is.
  • the upper layer 32 is preferably formed of a material having a total content of tantalum and silicon of 80 atomic% or more, more preferably 85 atomic% or more, and further preferably 90 atomic% or more.
  • the upper layer 32 may contain a metalloid element and a nonmetal element other than the above constituent elements as long as the above total content range is satisfied.
  • the metalloid element in this case include boron and germanium.
  • Nonmetallic elements in this case include nonmetallic elements in a narrow sense (oxygen, nitrogen, carbon, phosphorus, sulfur, selenium), halogens (fluorine, chlorine, etc.), noble gases (helium, neon, argon, krypton, xenon, etc.) .
  • the noble gas is an element that is slightly incorporated into the film when the upper layer 32 is formed by a sputtering method, and is also an element that may be beneficial when actively contained in the layer.
  • the upper layer 32 is obtained by dividing the metal content [atomic%] by the total content of metal and silicon [atomic%] (that is, the total content [M + Si] [atomic%] of metal and silicon in the upper layer 32 is 100).
  • the ratio of the metal content M [atomic%] when expressed as [%], hereinafter referred to as the M / [M + Si] ratio) is preferably 5% or more, and preferably 10% or more. And more preferably 15% or more.
  • the upper layer 32 preferably has an M / [M + Si] ratio of 60% or less, more preferably 55% or less, and even more preferably 50% or less.
  • a thin film of a metal silicide-based material has a tendency that the light shielding performance (optical density) increases as the content ratio of metal and silicon approaches a stoichiometrically stable ratio.
  • the ratio is stoichiometrically stable when metal: silicon is 1: 2, and the M / [M + Si] ratio of the upper layer 32 takes the tendency into consideration. It is what.
  • the thickness of the upper layer 32 is preferably 5 nm or more, more preferably 7 nm or more, and further preferably 10 nm or more. On the other hand, the thickness of the upper layer 32 is preferably 40 nm or less, more preferably 35 nm or less, and further preferably 30 nm or less.
  • the contribution of the upper layer 32 to the optical density required for the entire light shielding film 3 needs to be higher than the contribution of the lower layer 31. Further, there is a limit to increasing the optical density per unit film thickness of the upper layer 32.
  • the upper layer 32 since it is necessary for the upper layer 32 to be able to form a fine pattern by dry etching using a resist film having a fine pattern as a mask, there is a limit to increasing the thickness of the upper layer 32. .
  • the thickness range of the upper layer 32 takes these restrictions into consideration.
  • the upper layer 32 is preferably thinner than the lower layer 31.
  • the upper layer 32 forms a fine pattern by dry etching using a resist film on which a fine pattern is formed as a mask, but the surface of the upper layer 32 tends to have low adhesion with a resist film made of an organic material. For this reason, it is preferable that the surface of the upper layer 32 is subjected to HMDS (Hexamethyldisilazane) treatment to improve surface adhesion.
  • HMDS Hexamethyldisilazane
  • the extinction coefficient k U of the upper layer 32 of the light shielding film 3 is required to be larger than the extinction coefficient k L of the lower layer 31.
  • the extinction coefficient k L of the lower layer 31 is preferably 2.00 or less, more preferably 1.95 or less, and even more preferably 1.90 or less. Further, the extinction coefficient k L of the lower layer 31 is preferably 1.20 or more, more preferably 1.25 or more, and further preferably 1.30 or more. In contrast, the extinction coefficient k U of the upper layer 32 is preferably greater than 2.00, more preferable to be 2.10 or more and further preferably 2.20 or more. Further, the extinction coefficient k U of the upper layer 32 is preferably 3.20 or less, more preferable to be 3.10 or less, further preferably 3.00 or less.
  • the phase shift film 2 needs to have both a function of transmitting exposure light that is transmitted with a predetermined transmittance and a function of generating a predetermined phase difference. Since the phase shift film 2 is required to realize these functions with a thinner film thickness, the phase shift film 2 is often formed of a material having a high refractive index n.
  • the lower layer 31 of the light-shielding film 3 has a relatively high chromium content due to the above circumstances, and a low content of nitrogen, which is an element that tends to increase the refractive index n of the material when contained in the material. . For this reason, the lower layer 31 has a refractive index n smaller than that of the phase shift film 2.
  • the upper layer 32 of the light-shielding film 3 is required to greatly improve the light-shielding performance as described above. From these circumstances, the mask blank 100 has a laminated structure in which the refractive index n decreases in the order of the phase shift film 2, the lower layer 31, and the upper layer 32.
  • the exposure light traveling at a predetermined angle from the direction perpendicular to the interface of the phase shift film 2 enters the lower layer 31 of the light shielding film 3 from the phase shift film 2 with respect to the interface.
  • the inclination angle from the vertical direction will increase. Furthermore, when the exposure light that has entered the lower layer 31 enters the upper layer 32, the inclination angle from the direction perpendicular to the interface is further expanded.
  • the refractive index n U of the upper layer 32 is smaller than the refractive index n L of the lower layer 31 (i.e., the refractive index n U of the upper layer 32 in refractive index n L of the lower layer 31 less than divided by the ratio n U / n L is 1.0), the refractive index n U of the upper layer 32 the ratio n U / n L obtained by dividing the refractive index n L of the lower layer 31 is better to be a 0.8 or higher .
  • the ratio n U / n L obtained by dividing the refractive index n U of the upper layer 32 by the refractive index n L of the lower layer 31 is more preferably 0.85 or more, and further preferably 0.9 or more.
  • the refractive index n L of the lower layer 31 is preferably 2.00 or less, more preferably 1.98 or less, and even more preferably 1.95 or less. Further, the refractive index n L of the lower layer 31 is preferably 1.45 or more, more preferably 1.50 or more, and further preferably 1.55 or more. In contrast, the refractive index n U of the upper layer 32 is preferably less than 2.00, more preferable to be 1.95 or less, further preferably 1.90 or less. The refractive index n U of the upper layer 32 is preferably 1.30 or more, more preferably 1.35 or more and further preferably 1.40 or more.
  • the surface reflectance of the exposure light on both main surfaces of the phase shift mask is not too high in order to prevent exposure transfer defects due to reflection of ArF exposure light.
  • the reflectance on the surface side (surface farthest from the translucent substrate) of the light-shielding film, which receives the reflected light of the exposure light from the reduction optical system of the exposure apparatus is, for example, 60% or less (preferably 55%). It is desirable that This is to suppress stray light generated by multiple reflection between the surface of the light shielding film and the lens of the reduction optical system.
  • the thickness of the light-shielding film 3 in the laminated structure of the lower layer 31 and the upper layer 32 is preferably 80 nm or less, more preferably 75 nm or less, and further preferably 70 nm or less. Further, the thickness of the light-shielding film 3 in the laminated structure of the lower layer 31 and the upper layer 32 is preferably 30 nm or more, more preferably 35 nm or more, and further preferably 40 nm or more. If the entire thickness of the light shielding film 3 is too thick, it is difficult to form a fine pattern on the light shielding film 3 with high accuracy. On the other hand, if the total thickness of the light shielding film 3 is too thin, it is difficult for the light shielding film 3 to satisfy the required optical density.
  • the lower layer 31 and the upper layer 32 of the phase shift film 2 and the light shielding film 3 can be formed by sputtering.
  • Sputtering may be performed using a direct current (DC) power source or a radio frequency (RF) power source, and may be a magnetron sputtering method or a conventional method.
  • DC sputtering is preferred because the mechanism is simple.
  • the film forming apparatus may be an in-line type or a single-wafer type.
  • a resist film made of an organic material is preferably formed with a thickness of 100 nm or less in contact with the surface of the upper layer 32 of the light shielding film 3.
  • the upper layer 32 is formed of a material capable of patterning a fine pattern by dry etching with fluorine gas. Since the upper layer 32 functions as a hard mask at the time of dry etching with a mixed gas of chlorine-based gas and oxygen gas, which is performed when patterning a fine pattern on the lower layer 31, the light shielding film 3 even if the resist film is 100 nm or less. It is possible to form a fine pattern. More preferably, the resist film has a thickness of 80 nm or less.
  • the resist film is preferably a resist for electron beam drawing exposure, and more preferably, the resist is a chemical amplification type.
  • the mask blank 100 as described above has a high optical density suitable for SMO having an optical density of 3.5 or more with respect to the exposure light of the ArF excimer laser in the laminated structure of the phase shift film 2 and the light shielding film 3. For this reason, when a phase shift mask manufactured from the mask blank 100 is set in an exposure apparatus of a complicated illumination system to which SMO is applied, and exposure transfer is performed on a resist film to be transferred. In addition, the CD accuracy of the fine pattern formed on the resist film after the development process can be increased. Further, when a fine pattern is formed on the light shielding film 3 by dry etching, the mask blank 100 has a high CD accuracy of the formed fine pattern, and the formed fine pattern of the light shielding film 3 is tilted by cleaning or the like. Can be sufficiently suppressed.
  • the mask blank 100 having the above configuration is manufactured by the following procedure.
  • the translucent substrate 1 is prepared.
  • the translucent substrate 1 has its end face and main surface polished to a predetermined surface roughness (for example, a root mean square roughness Rq of 0.2 nm or less in a square inner region having a side of 1 ⁇ m), and then a predetermined surface roughness.
  • a predetermined surface roughness for example, a root mean square roughness Rq of 0.2 nm or less in a square inner region having a side of 1 ⁇ m
  • a phase shift film 2 is formed on the translucent substrate 1 by a sputtering method. After the phase shift film 2 is formed, an annealing process at a predetermined heating temperature is performed as a post process. Next, the lower layer 31 of the light shielding film 3 is formed on the phase shift film 2 by sputtering. Then, the upper layer 32 is formed on the lower layer 31 by sputtering. In the formation of each layer by sputtering, a sputtering target and a sputtering gas containing the material constituting each layer in a predetermined composition ratio are used, and if necessary, a mixed gas of the above-mentioned noble gas and reactive gas is sputtered. Film formation using gas is performed.
  • the mask blank 100 has a resist film
  • the surface of the upper layer 32 is subjected to HMDS treatment as necessary.
  • a resist film is formed on the surface of the upper layer 32 that has been subjected to the HMDS process by a coating method such as a spin coating method, and the mask blank 100 is completed.
  • HMDS treatment is performed on the surface of the upper layer 32 of the light shielding film 3 in the mask blank 100.
  • a resist film is formed on the upper layer 32 after the HMDS treatment by a spin coating method.
  • a first pattern (phase shift pattern, transfer pattern) to be formed on the phase shift film 2 is exposed and drawn on the resist film with an electron beam.
  • the resist film is subjected to predetermined processing such as PEB (post-exposure baking) processing, development processing, post-baking processing, and the like to form a first pattern (phase shift pattern) (resist pattern 4a) on the resist film ( (See FIG. 2 (a)).
  • PEB post-exposure baking
  • the upper layer 32 of the light shielding film 3 is dry-etched using a fluorine-based gas to form a first pattern (upper layer pattern 32a) on the upper layer 32 (see FIG. 2B). ). Thereafter, the resist pattern 4a is removed (see FIG. 2C).
  • dry etching of the lower layer 31 of the light-shielding film 3 may be performed with the resist pattern 4a remaining without being removed. In this case, the resist pattern 4a disappears when the lower layer 31 is dry etched.
  • the dry etching for the lower layer 31 uses an etching gas having a higher mixing ratio of chlorine-based gas than conventional.
  • the anisotropy of dry etching can be increased.
  • the bias voltage applied from the back side of the translucent substrate 1 is also made higher than before.
  • the power when applying this bias voltage is preferably 15 [W] or more, more preferably 20 [W] or more, and 30 [W] or more is more preferable.
  • a resist film is formed on the upper layer pattern 32a and the phase shift film 2 by a spin coating method.
  • a second pattern (a pattern including a light shielding band pattern) to be formed on the light shielding film 3 is exposed and drawn on the resist film with an electron beam.
  • a predetermined process such as a development process is performed to form a resist film having a second pattern (light-shielding pattern) (resist pattern 5b) (see FIG. 2E).
  • etching using a fluorine-based gas is performed to form a first pattern (phase shift pattern 2a) on the phase shift film 2 using the lower layer pattern 31a as a mask, and to the upper layer pattern 32a using the resist pattern 5b as a mask.
  • a second pattern (upper layer pattern 32b) is formed (see FIG. 2F).
  • the resist pattern 5b is removed.
  • a second pattern (lower layer pattern 31b) in the lower layer pattern 31a (FIG. 2G). (See (h)).
  • the dry etching of the lower layer pattern 31a may be performed under the conventional conditions of the mixing ratio of the chlorine-based gas and the oxygen gas and the bias voltage.
  • a phase shift mask 200 is obtained through a predetermined process such as cleaning (see FIG. 2H).
  • the chlorine-based gas used in the dry etching during the manufacturing process is not particularly limited as long as it contains Cl.
  • a chlorine-based gas Cl 2, SiH 2 Cl 2 , CHCl 3, CH 2 Cl 2, CCl 4, BCl 3 and the like.
  • the fluorine-based gas used in the dry etching in the manufacturing process is not particularly limited as long as F is contained.
  • a fluorine-based gas CHF 3, CF 4, C 2 F 6, C 4 F 8, SF 6 and the like.
  • the fluorine-based gas not containing C has a relatively low etching rate with respect to the glass substrate, damage to the glass substrate can be further reduced.
  • the phase shift film (phase shift pattern 2a) having a transfer pattern and the light shielding film (light shielding pattern 3b) having a light shielding pattern are arranged in this order on the translucent substrate 1. It has a laminated structure (see FIG. 2 (h)). Since this phase shift mask is manufactured from the mask blank 100, it has the same characteristics as the mask blank 100. That is, the phase shift mask 200 is a phase shift mask having a structure in which a phase shift film 2 having a transfer pattern and a light shielding film 3 having a light shielding band pattern are laminated in this order on a light transmitting substrate 1.
  • the optical density of the ArF excimer laser with respect to the exposure light in the laminated structure of the shift film 2 and the light shielding film 3 is 3.5 or more, and the light shielding film 3 is formed by laminating the lower layer 31 and the upper layer 32 from the translucent substrate 1 side.
  • the lower layer 31 is made of a material containing chromium and having a total content of chromium, oxygen, nitrogen and carbon of 90 atomic% or more, and the upper layer 32 contains metal and silicon. It consists total content is 80 atomic% or more materials, the extinction coefficient k U with respect to the exposure light of the upper layer 32, especially greater than the extinction coefficient k L with respect to the exposure light of the lower layer 31 It is set to.
  • This phase shift mask 200 is manufactured using the mask blank 100. For this reason, this phase shift mask 200 is set in an exposure apparatus of a complicated illumination system to which SMO is applied, and development processing is performed even when exposure transfer is performed on a resist film to be transferred. The CD accuracy of a fine pattern formed on the subsequent resist film can be increased.
  • phase shift pattern 2a the transfer pattern of the phase shift mask 200 is exposed and transferred to the resist film on the semiconductor substrate using the phase shift mask 200 described above.
  • the manufacturing method of such a semiconductor device is performed as follows.
  • a substrate for forming a semiconductor device is prepared.
  • This substrate may be, for example, a semiconductor substrate, a substrate having a semiconductor thin film, or a microfabricated film formed thereon.
  • a resist film is formed on the prepared substrate, and the resist film is repeatedly subjected to reduced transfer exposure using the phase shift mask 200 described above. Thereby, the transfer pattern formed on the phase shift mask 200 is arranged without a gap with respect to the resist film.
  • the exposure apparatus used at this time is capable of irradiating ArF exposure light with an optimal illumination system to the phase shift mask 200 to which the phase shift pattern 2a is optimized by applying SMO.
  • the resist film to which the transfer pattern is exposed and transferred is developed to form a resist pattern, the surface pattern of the substrate is etched using this resist pattern as a mask, and impurities are introduced. . After the processing is completed, the resist pattern is removed.
  • the semiconductor device is completed by repeatedly performing the above processing on the substrate while exchanging the transfer mask, and further performing necessary processing.
  • an exposure apparatus that can irradiate ArF exposure light with a complex but optimal illumination system is applied to the phase shift mask 200 to which the phase shift pattern 2a is optimized by applying SMO.
  • the phase shift mask 200 has an optical density with respect to ArF exposure light of 3.5 or more, which is significantly higher than the conventional one, in the laminated structure of the phase shift pattern 2a and the light shielding pattern 3b constituting the light shielding band.
  • extinction coefficient k U of upper layer pattern 32b and 3b are larger than the extinction coefficient k L of the lower layer pattern 31b, and has a so as to sufficiently suppress constituting the leakage light from the light-shielding band.
  • the extinction coefficient k U of upper layer pattern 32b and 3b are larger than the extinction coefficient k L of the lower layer pattern 31b, and has a so as to sufficiently suppress constituting the leakage light from the light-shielding band.
  • Example 1 Manufacture of mask blanks
  • a translucent substrate 1 made of synthetic quartz glass having a main surface dimension of about 152 mm ⁇ about 152 mm and a thickness of about 6.35 mm was prepared.
  • the translucent substrate 1 has its end face and main surface polished to a predetermined surface roughness (root mean square roughness Rq of 0.2 nm or less), and then subjected to a predetermined cleaning process and drying process.
  • Argon (Ar), nitrogen (N 2 ), and helium (He) mixed gas as a sputtering gas by reactive sputtering (DC sputtering), a phase shift made of molybdenum, silicon, and nitrogen on the light-transmitting substrate 1 Film 2 was formed with a thickness of 69 nm.
  • a heat treatment for reducing the film stress of the phase shift film 2 and forming an oxide layer on the surface layer was performed on the translucent substrate 1 on which the phase shift film 2 was formed.
  • a heating furnace electric furnace
  • heat treatment was performed in the atmosphere at a heating temperature of 450 ° C. and a heating time of 1 hour.
  • a phase shift amount measuring apparatus MPM193, manufactured by Lasertec Corporation
  • the transmittance and phase difference of the phase shift film 2 after the heat treatment with respect to light having a wavelength of 193 nm were measured. As a result, the transmittance was 6.0% and the phase difference was It was 177.0 degrees (deg).
  • phase shift film 2 is formed in the DC sputtering apparatus, using a chromium (Cr) target, an argon (Ar), carbon dioxide (CO 2) and helium Reactive sputtering (DC sputtering) was performed in a mixed gas atmosphere of (He).
  • a chromium (Cr) target an argon (Ar), carbon dioxide (CO 2) and helium Reactive sputtering (DC sputtering) was performed in a mixed gas atmosphere of (He).
  • the lower layer 31 of the light-shielding film (CrOC film) 3 made of chromium, oxygen and carbon was formed in a thickness of 43 nm in contact with the phase shift film 2.
  • the translucent substrate 1 in which the phase shift film 2 and the lower layer 31 are laminated is placed in a single wafer DC sputtering apparatus, and a tantalum silicide (TaSi 2 ) target is used and argon (Ar) gas is sputtered.
  • the upper layer 32 of the light shielding film 3 made of tantalum and silicon was formed to a thickness of 8 nm on the lower layer 31 of the light shielding film 3 by DC sputtering.
  • the light-transmitting substrate 1 on which the lower layer (CrOC film) 31 and the upper layer (TaSi film) 32 were formed was subjected to heat treatment. Specifically, using a hot plate, heat treatment was performed in the atmosphere at a heating temperature of 280 ° C. and a heating time of 5 minutes. After the heat treatment, an ArF excimer having a laminated structure of the phase shift film 2 and the light-shielding film 3 is used for the translucent substrate 1 on which the phase shift film 2 and the light-shielding film 3 are laminated, using a spectrophotometer (Cary 4000 manufactured by Agilent Technologies) The optical density at the wavelength of the laser beam (about 193 nm) was measured and found to be 4.12. Further, the surface reflectance of the light shielding film 3 opposite to the phase shift film 2 was measured and found to be 51%. Finally, a predetermined cleaning process was performed to manufacture the mask blank 100 of Example 1.
  • a spectrophotometer Cary 4000 manufactured by Agilent Technologies
  • phase shift film 2 and the light shielding film 3 were laminated on the main surface of another translucent substrate 1 under the same conditions.
  • the phase shift film 2 and the light shielding film 3 of this mask blank were analyzed by X-ray photoelectron spectroscopy (XPS) (with RBS correction).
  • XPS X-ray photoelectron spectroscopy
  • the composition of the inner region excluding the surface layer (region from the surface opposite to the translucent substrate 1 to a depth of 3 nm) where oxidation of the phase shift film 2 proceeds is Mo: 6 atomic%, Si : 45 atomic%, N: 49 atomic%.
  • the composition of the lower layer 31 of the light-shielding film 3 is Cr: 71 atomic%, O: 15 atomic%, C: 14 atomic%, and the upper layer 32 is oxidized (opposite to the translucent substrate 1).
  • the composition of the inner region excluding the region from the side surface to a depth of 3 nm was Ta: 32 atomic% and Si: 68 atomic%.
  • the difference between the constituent elements in the thickness direction was 3 atomic% or less, and it was confirmed that there was substantially no composition gradient in the thickness direction.
  • the difference of each constituent element in the thickness direction in the inner region of the upper layer 32 was 3 atomic% or less, and it was confirmed that there was substantially no composition gradient in the thickness direction in the inner region.
  • the total content of tantalum (Ta) and silicon (Si) in the entire upper layer 32 was 80 atomic% or more.
  • the refractive index n and the extinction coefficient k for light having a wavelength of 193 nm in the lower layer 31 and the upper layer 32 of the light shielding film 3 were measured using a spectroscopic ellipsometer (M-2000D manufactured by JA Woollam).
  • M-2000D manufactured by JA Woollam
  • the refractive index n L at the wavelength 193 nm of the lower layer 31 is 1.82 and the extinction coefficient k L is 1.83
  • the refractive index n U at the wavelength 193 nm of the upper layer 32 is 1.78
  • the extinction coefficient k U. was 2.84.
  • the ratio n U / n L obtained by dividing the refractive index n U of the upper layer 32 at a wavelength of 193 nm by the refractive index n L of the lower layer 31 at a wavelength of 193 nm was 0.978.
  • the halftone phase shift mask 200 of Example 1 was manufactured by the following procedure. First, the surface of the upper layer 32 of the light shielding film 3 was subjected to HMDS treatment. Subsequently, a resist film made of a chemically amplified resist for electron beam drawing was formed with a film thickness of 100 nm in contact with the surface of the upper layer 32 by spin coating. Next, a first pattern which is a phase shift pattern to be formed on the phase shift film 2 is drawn on the resist film by electron beam, a predetermined development process and a cleaning process are performed, and the resist having the first pattern A pattern 4a was formed (see FIG. 2A). The first pattern drawn by exposure was optimized by applying SMO. Further, the first pattern has a fine pattern in the vicinity of the light shielding band, as indicated by p 1a to p 1d in FIG.
  • a resist film was formed on the upper layer pattern 32a and the phase shift film 2 by a spin coating method.
  • a second pattern (a pattern including a light shielding band pattern) to be formed on the light shielding film 3 was exposed and drawn with an electron beam on the resist film.
  • predetermined processing such as development processing was performed to form a resist film (resist pattern 5b) having a second pattern (light-shielding pattern) (see FIG. 2E).
  • phase shift mask 200 of Example 1 was subjected to mask inspection using a mask inspection apparatus (Teron 600 Series manufactured by KLA-Tencor), no defects were found in the phase shift pattern 2a. From this, it was confirmed that even the light-shielding film 3 having higher light-shielding performance than the conventional one sufficiently functions as a hard mask for forming the fine pattern of the resist pattern 4a on the phase shift film 2. Further, even if the total content of metal and silicon in the upper layer 32 is increased, it has high resistance to dry etching with a mixed gas of chlorine-based gas and oxygen gas that is performed when forming a fine pattern in the lower layer 31; It was confirmed that it functions as a hard mask.
  • the CD accuracy of the fine pattern formed on the phase shift film 2 is lowered, and the CD accuracy of the fine pattern formed on the phase shift film 2 has been concerned about the light shielding film 3 having higher light shielding performance than before. It has been confirmed that the problem of deterioration of the light shielding film and the occurrence of pattern collapse of the light shielding film 3 are not a problem at all, the CD accuracy of these fine patterns is high, and the occurrence of pattern collapse of the light shielding film 3 can be suppressed. .
  • the phase shift mask 200 of Example 1 is set on a mask stage of an exposure apparatus that can irradiate the phase shift mask 200 with ArF exposure light with an illumination system optimized by SMO, and a resist on a semiconductor substrate.
  • the film was repeatedly exposed and transferred in the arrangement as shown in FIG.
  • the resist film on the semiconductor substrate after exposure and transfer was subjected to development processing and the like to form a resist pattern.
  • the resist pattern was observed by SEM, it was confirmed that the resist pattern was formed with high CD accuracy.
  • the fine patterns p 1d , p 2c , p 3b , and p 4a in the vicinity of the image S 1234 in the region where the shading band shown in FIG. It was confirmed that it was formed. From this result, it can be said that the circuit pattern can be formed with high accuracy by dry etching using the resist pattern as a mask.
  • Example 2 Manufacture of mask blanks
  • the mask blank 100 of Example 2 was manufactured in the same procedure as in Example 1 except that the lower layer 31 of the light shielding film 3 was formed with a thickness of 18 nm and the upper layer 32 was formed with a thickness of 24 nm.
  • a spectrophotometer Cary 4000 manufactured by Agilent Technologies
  • the optical density at the wavelength of light (about 193 nm) of an ArF excimer laser having a laminated structure of the phase shift film 2 and the light shielding film 3. was 412.
  • the surface reflectance of the light shielding film 3 on the side opposite to the phase shift film 2 was measured and found to be 55%.
  • phase shift mask 200 of Example 2 was manufactured in the same procedure as in Example 1.
  • the phase shift mask 200 of the second embodiment is subjected to mask inspection with a mask inspection apparatus (Teron600 Series manufactured by KLA-Tencor), and no defect is found in the phase shift pattern 2a. It was. From this, the same thing as Example 1 has been confirmed.
  • the phase shift mask 200 of the second embodiment is applied to the mask stage of the exposure apparatus that can irradiate the phase shift mask 200 with ArF exposure light with an illumination system optimized by SMO.
  • the resist film on the semiconductor substrate was repeatedly exposed and transferred in an arrangement as shown in FIG.
  • the resist film on the semiconductor substrate after exposure and transfer was subjected to development processing and the like to form a resist pattern.
  • the resist pattern was observed by SEM, it was confirmed that the resist pattern was formed with high CD accuracy.
  • the fine patterns p 1d , p 2c , p 3b , and p 4a in the vicinity of the image S 1234 in the region where the shading band shown in FIG. It was confirmed that it was formed. From this result, it can be said that the circuit pattern can be formed with high accuracy by dry etching using the resist pattern as a mask.
  • Example 3 Manufacture of mask blanks
  • the mask blank 100 of Example 3 was manufactured in the same procedure as Example 1 except for the light shielding film 3.
  • the lower layer 32 is formed of a CrOCN film, and the thickness of the upper layer 31 is changed with the same composition as that of Example 1.
  • the translucent substrate 1 on which the phase shift film 2 is formed is installed in a single-wafer DC sputtering apparatus, and using a chromium (Cr) target, argon (Ar), carbon dioxide (CO 2 ).
  • Reactive sputtering (DC sputtering) in a mixed gas atmosphere of nitrogen (N 2 ) and helium (He) was performed.
  • the lower layer 31 of the light shielding film (CrOCN film) 3 made of chromium, oxygen, carbon and nitrogen was formed in a thickness of 43 nm in contact with the phase shift film 2.
  • the translucent substrate 1 in which the phase shift film 2 and the lower layer 31 are laminated is placed in a single wafer DC sputtering apparatus, and a tantalum silicide (TaSi 2 ) target is used and argon (Ar) gas is sputtered.
  • the upper layer 32 of the light shielding film 3 made of tantalum and silicon was formed to a thickness of 12 nm on the lower layer 31 of the light shielding film 3 by DC sputtering.
  • Example 1 a mask blank in which the phase shift film 2 and the light shielding film 3 were laminated on the main surface of another translucent substrate 1 under the same conditions was manufactured.
  • the lower layer 31 and the upper layer 32 of the mask blank of Example 3 were analyzed by X-ray photoelectron spectroscopy (with XPS and RBS correction).
  • the composition of the lower layer 31 was Cr: 55 atomic%, O: 22 atomic%, C: 12 atomic%, and N: 11 atomic%.
  • the difference of each constituent element in the thickness direction in the inner region of the lower layer 31 was 3 atomic% or less, and it was confirmed that there was substantially no composition gradient in the thickness direction in the inner region.
  • the upper layer 32 was almost the same as the upper layer 32 of Example 1.
  • the refractive index n and the extinction coefficient k for light having a wavelength of 193 nm in the lower layer 31 of the mask blank of Example 3 were measured using a spectroscopic ellipsometer (M-2000D manufactured by JA Woollam).
  • M-2000D manufactured by JA Woollam
  • the refractive index n L of the lower layer 31 at a wavelength of 193 nm was 1.93
  • the extinction coefficient k L was 1.50.
  • the upper layer 32 was almost the same as the upper layer of Example 1.
  • the ratio n U / n L obtained by dividing the refractive index n U of the upper layer 32 at a wavelength of 193 nm by the refractive index n L of the lower layer 31 at a wavelength of 193 nm was 0.922.
  • the optical density at the wavelength of light (about 193 nm) of the ArF excimer laser having the laminated structure of the phase shift film 2 and the light shielding film 3 was measured. It was 4.06 when measured. Further, the surface reflectance of the light shielding film 3 on the side opposite to the phase shift film 2 was measured and found to be 52%.
  • phase shift mask 200 of Example 3 was manufactured in the same procedure as in Example 1.
  • the phase shift mask 200 of the third embodiment is subjected to mask inspection with a mask inspection apparatus (Teron 600 Series manufactured by KLA-Tencor), and no defect is found in the phase shift pattern 2a. It was. From this, the same thing as Example 1 has been confirmed.
  • the phase shift mask 200 of the third embodiment is applied to a mask stage of an exposure apparatus that can irradiate the phase shift mask 200 with ArF exposure light by an illumination system optimized by SMO.
  • the resist film on the semiconductor substrate was repeatedly exposed and transferred in an arrangement as shown in FIG.
  • the resist film on the semiconductor substrate after exposure and transfer was subjected to development processing and the like to form a resist pattern.
  • the resist pattern was observed by SEM, it was confirmed that the resist pattern was formed with high CD accuracy.
  • the fine patterns p 1d , p 2c , p 3b , and p 4a in the vicinity of the image S 1234 in the region where the shading band shown in FIG. It was confirmed that it was formed. From this result, it can be said that the circuit pattern can be formed with high accuracy by dry etching using the resist film as a mask.
  • Comparative Example 1 Manufacture of mask blanks
  • the mask blank of Comparative Example 1 was manufactured in the same procedure as in Example 1 except for the light shielding film 3.
  • the lower layer is formed of a CrOCN film and the upper layer is formed of a SiO 2 film.
  • a translucent substrate on which a phase shift film is formed is installed in a single-wafer DC sputtering apparatus, and using a chromium (Cr) target, argon (Ar), carbon dioxide (CO 2 ), nitrogen Reactive sputtering (DC sputtering) was performed in a mixed gas atmosphere of (N 2 ) and helium (He).
  • Cr chromium
  • Ar argon
  • CO 2 carbon dioxide
  • DC sputtering nitrogen Reactive sputtering
  • a lower layer of a light shielding film (CrOCN film) made of chromium, oxygen, and carbon was formed in a thickness of 43 nm in contact with the phase shift film.
  • a translucent substrate in which a lower layer of a phase shift film and a light shielding film is stacked is installed in a single wafer RF sputtering apparatus, and a silicon dioxide (SiO 2 ) target is used, and argon (Ar) gas is sputtered.
  • the upper layer of the light shielding film made of silicon and oxygen was formed to a thickness of 12 nm on the lower layer of the light shielding film by RF sputtering.
  • Example 2 In the same manner as in Example 1, a mask blank in which a phase shift film and a light-shielding film were laminated on the main surface of another translucent substrate under the same conditions was manufactured.
  • the lower layer and the upper layer of the light shielding film of the mask blank in Comparative Example 1 were analyzed by X-ray photoelectron spectroscopy (with XPS and RBS correction).
  • the composition of the lower layer is Cr: 55 atomic%, O: 22 atomic%, C: 12 atomic%, N: 11 atomic%
  • the composition of the upper layer is Si: 35 atomic%, O: 65 atomic% Met.
  • the difference of each constituent element in the thickness direction in the inner region of the lower layer and the upper layer was 3 atomic% or less, and it was confirmed that there was substantially no composition gradient in the thickness direction in the inner region.
  • the refractive index n and extinction coefficient k for light having a wavelength of 193 nm in the lower layer of the mask blank of Comparative Example 1 were measured using a spectroscopic ellipsometer (M-2000D manufactured by JA Woollam). did.
  • the refractive index n L at the lower layer wavelength of 193 nm was 1.93, and the extinction coefficient k L was 1.50.
  • the refractive index n U in the upper layer of the wavelength of 193nm is 1.59, extinction coefficient k U was 0.00.
  • the ratio n U / n L obtained by dividing the refractive index n U of the upper layer 32 at a wavelength of 193 nm by the refractive index n L of the lower layer 31 at a wavelength of 193 nm was 0.824.
  • an optical density at a wavelength of light (about 193 nm) of an ArF excimer laser having a laminated structure of a phase shift film and a light shielding film was measured using a spectrophotometer (Cary4000 manufactured by Agilent Technologies). However, it was 3.01. Further, when the surface reflectance of the light shielding film on the side opposite to the phase shift film was measured, it was 11%.
  • the phase shift mask 200 of Comparative Example 1 was manufactured in the same procedure as in Example 1.
  • a mask inspection was performed on the phase shift mask of Comparative Example 1 using a mask inspection apparatus (Teron600 Series manufactured by KLA-Tencor)
  • no defects were found in the phase shift pattern 2a.
  • the light-shielding film 3 having the same light-shielding performance thickness is also equivalent to the conventional one
  • the light-shielding performance is not increased by the composition, and the optical density is not secured by increasing the thickness. It was confirmed that it sufficiently functions as a hard mask for forming the fine pattern of the resist pattern 4a on the phase shift film.
  • the phase shift mask of the first comparative example is applied to the mask stage of the exposure apparatus that can irradiate the phase shift mask 200 with ArF exposure light with an illumination system optimized by SMO.
  • the resist film on the semiconductor substrate was set and repeatedly exposed and transferred in an arrangement as shown in FIG.
  • the resist film on the semiconductor substrate after exposure and transfer was subjected to development processing and the like to form a resist pattern.
  • the fine pattern p 1d , p 2c , p 3b in the vicinity of the image S 1234 in the region where the shading band shown in FIG. , P 4a was found to have particularly low CD accuracy. From this result, it can be said that when a circuit pattern is formed by dry etching using this resist film as a mask, a circuit defect or the like may occur.
  • Phase shift film 2a Phase shift pattern 3 Light shielding film 31 Lower layer 32 Upper layer 3b Light shielding pattern 31a, 31b Lower layer pattern 32a, 32b Upper layer pattern 4a, 5b Resist pattern 100 Mask blank 200 Phase shift mask

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